Treatment of textile materials



Patented June 2t, 1938 2,l2l,3il3

Ea'llilllEN'l iii TIEKTHLIE ma'ruamas llenry lllireyius, London, England No Dray. Application reh 2t, 1936, Serial No. 'll1,4l56. in great Britain ilpril 12, 1935 it iulaims.

Artificial'silk of reduced lustre may be obtained by forming it from spinning solutions containing in suspension very finely divided white in- 10 soluble compounds, for example titanium dioxide.

While this method yields materials of very satisfactory properties, it is open to theobjection that the materials of reduced lustre must be specially spun, and of course it is inapplicable in case it .5 isdesired to reduce the lustre of already spun materials. Obviously processes whereby already spun artificial silk may have its lustre reduced are very valuable.

Ill have found that textile materials having wayo tor-insoluble titanium compounds fixed therein "may be produced with the a'id or the double ammonium titanium salts of weak poly-basic acids (including di-basic acids), especially of carbonic acid or poly-basic organic acids (including dibasic organic acids). As examples of such salts I may instance ammonium titanium tartrate and the ammonium titanium carbonate obtainable by adding a solution of a. titanium salt, such as titanium chloride or sulphate, to a solution of am- 30 monium carbonate largely in excess of that which would be capable of converting the titanium salt into titanium dioxide. These double ammonium titanium salts may very readily be decomposed with formation of titanium dioxide, for example 5, by heat in the presence of moisture or steam containing a little ammonia.

According to my invention I produce textile materials, particularly artificial silk, having waher-insoluble titanium compounds fixed therein,

49 by impregnating the appropriate textile material with one of the aforesaid double ammonium titanium salts, and thereafter decomposingthe'salt with formation of titanium oxide (which may be hydrated) or other water-insoluble titanium com- 45 pound in the material. In this way cellulose acetate or other artificial silk of low lustre may be obtained from already spun artificial silk of normal lustre. K

As examples of double ammonium titanium o salts which may be employed in the new process i may be mentioned, in addition to the ammonium (tlll. Ed -ll) nium tartrate may be obtained by dissolving titanic acid in acid ammonium tartrate. Similarly ammonium titanium citrate may be obtained from titanic acid and acid ammonium citrate.

If desired, ammonium titanium carbonate ma be prepared by dissolving already prepared titanic acid in a solution of ammonium carbonate. Thus titanic acid may be precipitated from a titanium chloride or sulphate solution with ammonia, ammonium carbonate, or other alkali, freed whol- 1y or in part from soluble salts, and dissolved in ammonium carbonate solution.

The double ammonium titanium carbonate is of particular value in that it may be decomposed in or on a textile material, by the action of heat. e. g. by steaming, or by evaporation of its aqueous solutions, with the production, apart from the titanium dioxide, of volatile decomposition products only, namely ammonia and carbon dioxide. These are very readily eliminated from the textile material, so that by impregnating a textile material with a solution containing the ammonium titanium carbonate and drying, textile material containing titanium dioxide and free from other decomposition products is directly obtained.

Instead of the double ammonium titanium salts analogous salts in which the ammonia is replaced by a volatile nitrogenous organic base, for example methylamine or ethylamine, may be employed.

Further, -by using instead of titanium com: poundscorresponding double compounds of the similar metals of group IV offthe periodic classification, for example tin, textile materials hav-' ing compounds of such other metals fixed therein for mordanting, weighting, or other purposes. may be produced in accordance with the invention. For the fixation of tin compounds for example, there may be employed ammonium stannic oxalate, (NH4)2SI1(C2O4)2, or stannic ammonium citrate obtained, for instance, by dissolving hydrated tin oxide in ammonium citrate.

Various methods may be utilized for the application of the titanium or other compounds to the materials and for their decomposition thereon. Preferably solutions of the titanium or other compounds are applied to the materials in predetermined quantities, especially by padding,

spraying, printing or other form of mechanical impregnation. Spraying, printing and the like may be utilized to produce local effects on the materials, for example difierential lustre eflects. Padding and spraying are-particularly convenient, though predetermined quantities of the solutions may also be applied by impregnating the pound on the material may be eflected by drying alone, for example at temperatures of the order of C., where the compound is one readily' decomposable as in the case of the above-mentioned ammonium titanium carbonate. Another method of effecting the desired decomposition is to steam the impregnated materials or to treat them with gaseous alkalies, for example ammonia or a volatile organic base such as methylamine.

If desired, ammonia or other volatile alkali may be employed in conjunction with steam in the manner described in U. S. application S. No. 30,945'illed 11th July 1935. A further, though less preferable, method of decomposing the titanium or other compound is to subject the impregnated material to the action of an aqueous solution of a suitable reagent. Thus textile material impregnated with an ammonium titanium or ammonium tin compound of oxalic or tartaric acid or other dior poly-basic organic acid, may be subjected to a bath treatment with an aqueous solution of an alkaline material. Alternatively the aqueous solution of the alkaline material may 35 be applied by mechanical impregnation methods.

The process of the present invention maybe carried out continuously, fabric, yarn, or other textile material being carried continuously through an impregnating bath or padding mangle and thereafter subjected to an appropriate treatment for decomposition of the titanium or other compound on the material. Decomposition by drying, steam, or steam in conjunction with a volatile alkali, is particularly convenient in such a continuous process.

The invention is of-general application for the fixation of titanium or? like metal compounds on textile materials. Itf'is, however, particularly suitable for reducing. the lustre of artificial silk,

agents for the materials may be incorporated in the solutions. An alternative is to pretreat the materials with such wetting or swelling agents. As examples of swelling agents for cellulose ester or ether materials may be mentioned alkali or alkaline earth or other soluble thiocyanates, or organic swelling agents, for instance ethyl or other alcohol, acetone or other ketone, cyclic ethers, glycol-ethers or esters or ether-esters, or

. aromatic hydroxy compounds, suitably diluted if necessary. The titanium or other salt may itself be capable of swelling the material, for instance a double salt of ammonia and titanium with an organic acid, e. g. oxalic acid or tartaric acid may be employed in a concentration sui'iicient to swell cellulose acetate or other cellulose ester or ether.-

The materials treated in accordance with the new process may be given an aqueous scouring treatment in order to remove any water-soluble compound remaining on or in the materials.

It is to be understood that the term salt of a The following examples illustrate the invention but are not to be considered as limiting it in any way:

Example 1 An aqueous liquid is prepared containing 5% of diethylene glycol and ammonium titanium tartrate in quantity equivalent to 2.5% of tita-.

nium dioxide. A fabric of lustrous cellulose acetate yarns ispaxided with this solution, the padding mangle being adjusted so that the material retains about of its weight of the padding liquor. The material is then steamed for 10 minutes with moist steam maintained slightly alkaline with ammonia. The fabric is thereafter washed and dried. By this treatment the lustre of the fabric is very considerably reduced.

Fabrics of lustrous regenerated cellulose artificial silk may be treated inra similar manner. In this case the diethylene glycol may be omitted.

Stannic oxide may similarly be fixed in artificial silk by substituting stannic ammonium oxalate-or stannic ammonium citrate for the tita nium compound specified in this example.

Example 2 A fabric of lustrous regenerated cellulose artiflcial silk is padded with a solution of titanium ammonium carbonate having a titanium content equivalent to 1.5% of titanium dioxide. The padding mangle is adjust'edso that the fabric retains about 150% of its weight of the padding liquor. The material is then dried or steamed in order to produce titanium dioxide 'on the material, whereby the lustre of the latter is substantially reduced.

Having described my invention what I desire to secure by Letters Patent is: L

1. Process'of reducing the lustre of artificial silk, which comprises impregnating it with a double salt of a poly-basic organic acid with ammonia and titanium, and then thermally decomposing the salt with formation of titanium dioxide on the material.

,2. Process of reducing the lustre of artificial silk, which comprises impregnating it with titanium ammonium carbonate and then decomposing the carbonate with formation of titanium dioxide on the material.

. 3. Process of reducing the lustre of cellulose acetate artificial silk, which comprises impregnating it witha double salt gt a poly-basicorganic acid with ammonia and titanium, and then thermally decomposing the salt with formation' of titanium dioxide on the material.

4. Process of reducing't-he lustre of cellulose acetate artificial silk, which comprises impregnating it with titanium ammonium carbonate and then decomposing the carbonate with for- .mation of titanium dioxide on the material.

5. Process of reducing the lustre of cellulose acetate artificial silk, which comprises impregnating it with titanium ammonium tartrate and subjecting the impregnated material to the action of steam and ammonia so as to decompose the tartrate with formation of titan'ium dioxide on prises impregnating the materials with a double salt of a polybasic organic acid with titanium and a volatile nitrogenous base, and then decomposing the double salt with the formation of L the insoluble titanium compound in the materials.

8. Process for incorporating a water-insoluble titanium compound in textile materials, which comprises impregnating the materials with a double salt of a polybasic organic acid with titanium and a volatile nitrogenous base, and then thermally decomposing the double salt with the formation of the insoluble titanium compound in the materials.

9. Process for delustering' textile materials, which comprises impregnating the materials with a double salt of a polybasic organic acid with titanium and a volatile nitrogenous base, and then thermally decomposing the double salt with the formation of titanium dioxide in the materials.

10; Process for delustering textile materials comprising cellulose acetate artificial silk, which comprises impregnating the materials with a double salt of a polybasic organic acid with titanium and a volatile nitrogenous base, and then thermally decomposing the double salt with the 20 formation of titanium dioxide in the materials.

HENRY DREYFUSI. 

